PCTFE blow molding containers

ABSTRACT

Molded articles which include at least one layer of a fluoropolymer and at least one layer of a thermoplastic polymer. More particularly, molded bottles having a layer of a fluoropolymer attached to a layer of a polyethylene via an intermediate adhesive tie layer. The molded articles are preferably formed such that the fluoropolymer layer is either the innermost layer or central layer of the multilayered structure. The adhesives that are employed are useful in adhering layers of dissimilar polymeric materials that are otherwise incompatible and achieve a significantly improved interlayer bond strength between a fluoropolymer layer and a thermoplastic polymer layer.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to shaped articles including a layer of afluoropolymer and a layer of a thermoplastic polymer. More particularly,the invention pertains to molded articles, particularly molded bottles,having a layer of a fluoropolymer attached to a layer of a polyethylenevia an intermediate adhesive. The adhesives that are employed are usefulin adhering layers of dissimilar polymeric materials that are otherwiseincompatible and achieve a significantly improved interlayer bondstrength between a fluoropolymer layer and a thermoplastic polymerlayer.

2. Description of the Related Art

A wide variety of thermoplastic polymers and bottle containers formedfrom such thermoplastic polymers are known. Important physicalcharacteristics of such a container includes its barrier properties,including barriers to gas, aroma, and/or vapor such as water vapor, aswell as its physical characteristics, such as toughness, clarity, wearand weathering resistances, light-transmittance and chemical inertness.These properties are especially important in packaging applications forfood or medical products.

It is well known in the art to produce multilayer fluoropolymer films.See, for example, U.S. Pat. Nos. 4,146,521; 4,659,625; 4,677,017;5,139,878; 5,855,977; 6,096,428; 6,138,830; and 6,197,393. Manyfluoropolymer materials are commonly known for their excellent moistureand vapor barrier properties, as well as their chemical resistance, andtherefore are desirable components of packaging articles, particularlylidding films, blister packages and bottle containers. In addition,fluoropolymers exhibit high thermal stability and excellent toughness.However, such use of fluoropolymers is restricted to specialty packagingapplications due to their relatively high cost. A suitable means ofreducing the cost of a packaging material fabricated from a costlypolymer is to form multilayer structures in which the polymer islaminated with other, less costly polymer layers. This approach isparticularly desirable for the fluoropolymer packaging applicationssince a thin layer of the fluoropolymer is often all that is needed totake advantage of the desirable properties of the fluoropolymer whileminimizing the cost. However, fluoropolymers do not adhere strongly tomost other polymers. In fact, most fluoropolymers are known for theirnon-stick characteristics. This is very disadvantageous, because poorbond strength between layers can result in the delamination ofmultilayer structures.

To improve the bond strength between a layer of a fluoropolymer and alayer of a thermoplastic polymer (e.g. a non-fluoropolymer layer), anadhesive tie layer may be used between adjacent layers. For example,U.S. Pat. No. 4,677,017 discloses coextruded multilayer films whichinclude at least one fluoropolymer film and at least one thermoplasticfilm which are joined by the use of an adhesive polymer, particularlyethylene/vinyl acetate polymers, as an adhesive tie layer. U.S. Pat. No.4,659,625 discloses a fluoropolymer multilayer film structure whichutilizes a vinyl acetate polymer adhesive tie layer. U.S. Pat. No.5,139,878, discloses a fluoropolymer film structure using an adhesivetie layer of modified polyolefins. U.S. Pat. No. 6,451,925 teaches alaminate of a fluoropolymer layer and a non-fluoropolymer layer using anadhesive tie layer which is a blend of an aliphatic polyamide and afluorine-containing graft polymer. Additionally, U.S. Pat. No. 5,855,977teaches applying an aliphatic di- or polyamine to one or more surfacesof a fluoropolymer or non-fluoropolymer material layer.

As an alternative to an adhesive tie layer, a surface treatment of oneor both of the layers has been used to increase the adhesive bondstrength between the two dissimilar layers. For example, U.S. Pat. No.6,197,393 describes treating a non-fluoropolymer layer by providing abonding composition which comprises a primary or secondary di- orpolyamine and a non-fluorinated base polymer, and then reacting thesecomponents to form an amine-functionalized base polymer, which basepolymer materials may include polyamides, polyamide imides, polyetherimides, polyimides, polyureas, polyurethanes, polyesters,polycarbonates, functionalized polyolefins and polyketones. This is thencompounded with a second different non-fluorinated polymer to form ablend layer. The blend layer may then be processed with a fluoropolymerlayer to form multilayered articles or structures. Additionally, U.S.Pat. No. 6,096,428 teaches the step of blending a carboxyl, carboxylate,anhydride, amide, imide, hydroxyl, or oxycarbonyl functional polyolefinwith an organic or inorganic base and an organo-onium compound, forminga non-fluorinated polymeric material. This non-fluorinated material isthen capable of being laminated to a fluoropolymer layer under heat andpressure, and formed into articles or structures. U.S. Pat. No.5,855,977 teaches a multilayered structure having a fluoropolymer layerand a non-fluorinated polymeric layer that has an aliphatic di- orpolyamine present.

There is a continuing need in the art for further improvements in moldedarticles formed from fluoropolymers. Particularly desirable arelightweight, non-breakable structures with good clarity, a high moisturebarrier, good chemical resistance and low water vapor and gastransmission. More particularly, there is a need in the art for articlesformed from fluoropolymers, which articles have good properties that areacceptable for storing moisture sensitive products. Such propertiesinclude providing chemical resistance, improved product shelf life andeliminating the breakage concerns of glass containers. The presentinvention satisfies this need in the art. The invention provides shapedarticles for storing products which articles are formed in afluoropolymer-containing multilayer structure that exhibits excellentbond strength between a fluoropolymer layer and a thermoplastic polymerlayer.

SUMMARY OF THE INVENTION

The invention provides a shaped article for storing a product, saidshaped article being formed from a multilayered structure whichcomprises in sequence:

-   -   a) an inner fluoropolymer layer having first and second        surfaces;    -   b) an adhesive tie layer, having first and second surfaces, on        the inner fluoropolymer layer with the first surface of the        adhesive tie layer on the first surface of the fluoropolymer        layer; which adhesive tie layer comprises a combination of at        least one tackifier, at least one ethylene/alpha-olefin        copolymer and optionally at least one styrenic block copolymer;        and    -   c) an outer thermoplastic polymer layer, having first and second        surfaces, on the adhesive tie layer with the first surface of        the thermoplastic polymer layer on the second surface of the        adhesive tie layer.

The invention also provides a shaped article for storing a product, saidshaped article being formed from a multilayered structure whichcomprises in sequence:

-   -   a) an inner poly(chlorotrifluoroethylene) layer having first and        second surfaces;    -   b) an adhesive tie layer, having first and second surfaces, on        the inner poly(chlorotrifluoroethylene) layer with the first        surface of the adhesive tie layer on the first surface of the        poly(chlorotrifluoroethylene) layer; which adhesive tie layer        comprises a combination of at least one tackifier, at least one        ethylene/alpha-olefin copolymer and optionally at least one        styrenic block copolymer;    -   c) a polyethylene layer, having first and second surfaces, on        the adhesive tie layer with the first surface of the        polyethylene layer on the second surface of the adhesive tie        layer; and    -   d) at least one polymer layer on the second surface of the        polyethylene layer.

The invention further provides a process for forming a shaped articlefor storing a product which comprises:

-   -   I) forming a multilayered structure by a process which        comprises:        -   a) forming an inner fluoropolymer layer having first and            second surfaces;        -   b) attaching an adhesive tie layer, having first and second            surfaces, to the fluoropolymer layer with the first surface            of the adhesive tie layer on the first surface of the            fluoropolymer layer; which adhesive tie layer comprises a            combination of at least one tackifier, at least one            ethylene/alpha-olefin copolymer and optionally at least one            styrenic block copolymer;        -   c) attaching an outer thermoplastic polymer layer, having            first and second surfaces, to the adhesive tie layer with            the first surface of the thermoplastic polymer layer on the            second surface of the adhesive tie layer; and    -   II) forming said multilayered structure into an article by        injection molding, blow molding, co-injection blow molding,        co-injection stretch-blow molding or co-extrusion blow molding        techniques.

The invention still further provides a shaped article for storing aproduct, said shaped article being formed from a multilayered structurewhich comprises in sequence:

-   -   a) a first outer thermoplastic polymer layer, having first and        second surfaces;    -   b) a first adhesive tie layer, having first and second surfaces,        on the first outer thermoplastic layer with the first surface of        the first adhesive tie layer on the first surface of the first        outer thermoplastic polymer layer; which first adhesive tie        layer comprises a combination of at least one tackifier, at        least one ethylene/alpha-olefin copolymer and optionally at        least one styrenic block copolymer; and    -   c) a central fluoropolymer layer having first and second        surfaces, on the first adhesive tie layer with the first surface        of the central fluoropolymer layer on the second surface of the        first adhesive tie layer;    -   d) a second adhesive tie layer, having first and second        surfaces, on the central fluoropolymer layer with the first        surface of the second adhesive tie layer on the first surface of        the central fluoropolymer layer; which second adhesive tie layer        comprises a combination of at least one tackifier, at least one        ethylene/alpha-olefin copolymer and optionally at least one        styrenic block copolymer; and    -   e) a second outer thermoplastic polymer layer, having first and        second surfaces, on the second adhesive tie layer with the first        surface of the second outer thermoplastic polymer layer on the        second surface of the second adhesive tie layer.

The invention also provides a shaped article for storing a product, saidshaped article being formed from a multilayered structure whichcomprises in sequence:

-   -   a) a first outer polyethylene layer, having first and second        surfaces;    -   b) a first adhesive tie layer, having first and second surfaces,        on the first outer polyethylene layer with the first surface of        the first adhesive tie layer on the first surface of the first        outer polyethylene layer; which first adhesive tie layer        comprises a combination of at least one tackifier, at least one        ethylene/alpha-olefin copolymer and optionally at least one        styrenic block copolymer; and    -   c) a central poly(chlorotrifluoroethylene) layer having first        and second surfaces, on the first adhesive tie layer with the        first surface of the central poly(chlorotrifluoroethylene) layer        on the second surface of the first adhesive tie layer;    -   d) a second adhesive tie layer, having first and second        surfaces, on the central poly(chlorotrifluoroethylene) layer        with the first surface of the second adhesive tie layer on the        first surface of the central poly(chlorotrifluoroethylene)        layer; which second adhesive tie layer comprises a combination        of at least one tackifier, at least one ethylene/alpha-olefin        copolymer and optionally at least one styrenic block copolymer;        and    -   e) a second outer polyethylene layer, having first and second        surfaces, on the second adhesive tie layer with the first        surface of the second outer polyethylene layer on the second        surface of the second adhesive tie layer.

The invention further provides a process for forming a shaped articlefor storing a product which comprises:

-   -   I) forming a multilayered structure by a process which        comprises:        -   a) forming a first outer thermoplastic polymer layer, having            first and second surfaces;        -   b) attaching a first adhesive tie layer, having first and            second surfaces, to the first outer thermoplastic layer with            the first surface of the first adhesive tie layer on the            first surface of the first outer thermoplastic polymer            layer; which first adhesive tie layer comprises a            combination of at least one tackifier, at least one            ethylene/alpha-olefin copolymer and optionally at least one            styrenic block copolymer; and        -   c) attaching a central fluoropolymer layer having first and            second surfaces, to the first adhesive tie layer with the            first surface of the central fluoropolymer layer on the            second surface of the first adhesive tie layer;        -   d) attaching a second adhesive tie layer, having first and            second surfaces, to the central fluoropolymer layer with the            first surface of the second adhesive tie layer on the first            surface of the central fluoropolymer layer; which second            adhesive tie layer comprises a combination of at least one            tackifier, at least one ethylene/alpha-olefin copolymer and            optionally at least one styrenic block copolymer; and        -   e) attaching a second outer thermoplastic polymer layer,            having first and second surfaces, to the second adhesive tie            layer with the first surface of the second outer            thermoplastic polymer layer on the second surface of the            second adhesive tie layer; and    -   II) forming said multilayered structure into an article by        injection molding, co-injection blow molding, co-injection        stretch-blow molding or co-extrusion blow molding techniques.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a cross-sectional side-view of a shaped article of theinvention which contains a liquid product.

FIG. 2 is a cross-sectional side-view of a shaped article of theinvention that contains a solid product which product is adjacent to aninner fluoropolymer layer.

FIG. 3 is a plan-view, schematic representation of a multilayeredstructure of the invention having an inner fluoropolymer layer attachedto an outer thermoplastic polymer layer via an adhesive tie layer of theinvention and further having a polymer layer attached to the outerthermoplastic polymer layer via another adhesive tie layer.

FIG. 4 is a plan-view, schematic representation of a multilayeredstructure of the invention having multiple additional polymeric layersattached to said outer thermoplastic polymer layer.

FIG. 5 is a plan-view, schematic representation of a multilayeredstructure of the invention having a central fluoropolymer layer, anadhesive tie layer on either side of the central fluoropolymer layer anda plurality of polymer layers attached to the outer thermoplasticpolymer layer via additional adhesive layers.

FIG. 6 is a cross sectional side-view of a shaped article of theinvention that contains a liquid-product with the shaped article beingformed from a multilayered structure having a central fluoropolymerlayer, an adhesive tie layer on either side of the central fluoropolymerlayer and an outer thermoplastic polymer layer on each adhesive tielayer.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

As can be seen in FIG. 1, FIG. 2 and FIG. 6, the invention providesshaped articles 10 suitable for storing a product 20, which articles areformed from a multilayered structure such as those shown in FIG. 3through FIG. 5. In one embodiment of the invention, the multilayeredstructure of the invention includes an inner fluoropolymer layer 12attached to an outer thermoplastic polymer layer 14. These layers areattached by an intermediate adhesive tie layer 16 which is a combinationof at least one tackifier, at least one ethylene/alpha-olefin copolymerand optionally one or more styrenic block copolymers. This adhesive tielayer 16 imparts excellent bond strength between adjacent layers of thestructure and particularly between the fluoropolymer layer 12 and theouter thermoplastic polymer layer 14. Shaped articles, such as thoseillustrated in FIG. 1 and FIG. 2, are preferably formed from thismultilayered structure such that the fluoropolymer layer 12 is theinnermost layer of the article and is positioned adjacent to a productplaced inside the shaped article 10.

In an alternate embodiment of the invention, a second outerthermoplastic polymer layer 14 is attached to another surface of saidfluoropolymer layer 12 via a second intermediate adhesive tie layer 16such that the fluoropolymer layer is the central layer of themultilayered structure, being positioned between the two thermoplasticpolymer layers 14 and adhesive tie layers 16. This embodiment isillustrated in FIG. 5. FIG. 6 illustrates a shaped article formed fromthis type of multilayered structure.

With regard to the individual layers of the shaped articles 10 of theinvention, the inner or the central fluoropolymer layer 12 has first andsecond surfaces and is joined with an adhesive tie layer 16 such thatthe first surface of the inner fluoropolymer layer 12 is in contact witha first surface of the adhesive tie layer 16. Fluoropolymer materialsare commonly known for their excellent chemical resistance and excellentrelease properties, as well as their moisture and vapor barrierproperties. Accordingly, fluoropolymer materials are desirablecomponents for packaging applications. In the preferred embodiment ofthe invention, the fluoropolymer layer 12 may be comprised offluoropolymer homopolymers or copolymers or blends thereof as are wellknown in the art and are described in, for example, U.S. Pat. Nos.4,510,301, 4,544,721 and 5,139,878. Preferred fluoropolymers include,but are not limited to, homopolymers and copolymers ofchlorotrifluoroethylene, ethylene-chlorotrifluoroethylene copolymer,ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylenecopolymer, perfluoroalkoxyethylene, polychlorotrifluoroethylene,polytetrafluoroethylene, polyvinyl fluoride, polyvinylidene fluoride,and copolymers and blends thereof. As used herein, copolymers includepolymers having two or more monomer components. The most preferredfluoropolymers include homopolymers and copolymers ofpoly(chlorotrifluoroethylene). Particularly preferred are PCTFE(polychlorotrifluoroethylene homopolymer) materials sold under theACLON™ trademark and which are commercially available from HoneywellInternational Inc. of Morristown, N.J.

In the production of the shaped articles 10 of the invention, outerthermoplastic polymer layer 14 has first and second surfaces and isattached to the fluoropolymer layer 12 such that the first surface ofthe outer thermoplastic polymer layer 14 is in contact with the secondsurface of the adhesive tie layer 16. Suitable thermoplastic polymermaterials include non-fluoropolymer materials such as linear or branchedpolyolefin homopolymers, linear or branched polyolefin copolymers,cyclic olefin homopolymers, copolymers of cyclic olefins and linear orbranched polyolefin homopolymers, copolymers of cyclic olefins andlinear or branched polyolefin copolymers, ethylene vinyl acetatecopolymers, polyesters such as polyethylene terephthalate, polyamides,polyvinyl chloride, polyvinylidene chloride, polystyrene, styreniccopolymers, polyisoprene, polyurethanes, ethylene ethyl acrylate,ethylene acrylic acid copolymers and combinations thereof. Thethermoplastic polymer layer 14 may also comprise another fluoropolymerlayer. In the preferred embodiment of the invention, outer thermoplasticpolymer layer 14 comprises polyethylene.

Suitable polyolefins for use herein include polymers of alpha-olefinmonomers having from about 3 to about 20 carbon atoms and includehomopolymers, copolymers (including graft copolymers), and terpolymersof alpha-olefins. Illustrative homopolymer examples includepolyethylenes such as low density polyethylene (LDPE), ultra low densitypolyethylene (ULDPE), linear low density polyethylene (LLDPE),metallocene linear low density polyethylene (m-LLDPE), medium densitypolyethylene (MDPE), and high density polyethylene (HDPE). Alsopreferred are polypropylene, polybutylene, polybutene-1,poly-3-methylbutene-1, poly-pentene-1, poly-4,4 dimethylpentene-1,poly-3-methyl pentene-1, polyisobutylene, poly-4-methylhexene-1,poly-5-ethylhexene-1, poly-6-methylheptene-1, polyhexene-1,polyoctene-1, polynonene-1, polydecene-1, polydodecene-1 and the like.Also suitable are blends of these polyolefins.

Polyolefins such as polyethylenes are commonly differentiated based onthe density which results from their numbers of chain branches per 1,000carbon atoms in the polyethylene main chain in the molecular structure.Branches typically are C₃-C₈ olefins, more preferably propylene, butene,hexene or octene. For example, HDPE has very low numbers of short chainbranches (less than 20 per 1,000 carbon atoms), resulting in arelatively high density, i.e. density ranges from about 0.94 gm/cc toabout 0.97 gm/cc. LLDPE has more short chain branches, in the range of20 to 60 per 1,000 carbon atoms with a density of about 0.90 to about0.93 gm/cc. LDPE with a density of about 0.91 to about 0.93 gm/cc haslong chain branches (20-40 per 1,000 carbon atoms) instead of shortchain branches in LLDPE and HDPE. ULDPE has a higher concentration ofshort chain branches than LLDPE and HDPE, i.e. in the range of about 80to about 250 per 1,000 carbon atoms and has a density of from about 0.88to about 0.92 gm/cc. Illustrative copolymers and terpolymers includecopolymers and terpolymers of alpha-olefins with other olefins such asethylene-propylene copolymers; ethylene-butene copolymers;ethylene-pentene copolymers; ethylene-hexene copolymers; andethylene-propylene-diene copolymers (EPDM). The term polyolefin as usedherein also includes acrylonitrilebutadiene-styrene (ABS) polymers,copolymers with vinyl acetate, acrylates and methacrylates and the like.Preferred polyolefins are those prepared from alpha-olefins, mostpreferably ethylene polymers, copolymers, and terpolymers. The abovepolyolefins may be obtained by any known process. The polyolefin mayhave a weight average molecular weight of about 1,000 to about1,000,000, and preferably about 10,000 to about 500,000 as measured byhigh performance liquid chromatography (HPLC). Preferred polyolefins arepolyethylene, polypropylene, polybutylene and copolymers, and blendsthereof. The most preferred polyolefin is polyethylene. The mostpreferred polyethylenes are low density polyethylenes.

Suitable polyamides within the scope of the invention non-exclusivelyinclude homopolymers or copolymers selected from aliphatic polyamidesand aliphatic/aromatic polyamides having a weight average molecularweight of from about 10,000 to about 100,000. General procedures usefulfor the preparation of polyamides are well known to the art. Suchinclude the reaction products of diacids with diamines. Useful diacidsfor making polyamides include dicarboxylic acids which are representedby the general formulaHOOC-Z-COOHwherein Z is representative of a divalent aliphatic radical containingat least 2 carbon atoms, such as adipic acid, sebacic acid,octadecanedioic acid, pimelic acid, suberic acid, azelaic acid,dodecanedioic acid, and glutaric acid. The dicarboxylic acids may bealiphatic acids, or aromatic acids such as isophthalic acid andterephthalic acid. Suitable diamines for making polyamides include thosehaving the formulaH₂N(CH₂)_(n)NH₂wherein n has an integer value of 1-16, and includes such compounds astrimethylenediamine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, octamethylenediamine, decamethylenediamine,dodecamethylenediamine, hexadecamethylenediamine, aromatic diamines suchas p-phenylenediamine, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenylsulphone, 4,4′-diaminodiphenylmethane, alkylated diamines such as2,2-dimethylpentamethylenediamine, 2,2,4-trimethylhexamethylenediamine,and 2,4,4 trimethylpentamethylenediamine, as well as cycloaliphaticdiamines, such as diaminodicyclohexylmethane, and other compounds. Otheruseful diamines include heptamethylenediamine, nonamethylenediamine, andthe like.

Useful polyamide homopolymers include poly(4-aminobutyric acid) (nylon4), poly(6-aminohexanoic acid) (nylon 6, also known aspoly(caprolactam)), poly(7-aminoheptanoic acid) (nylon 7),poly(8-aminooctanoic acid)(nylon 8), poly(9-aminononanoic acid) (nylon9), poly(10-aminodecanoic acid) (nylon 10), poly(11-aminoundecanoicacid) (nylon 11) and poly(12-aminododecanoic acid) (nylon 12), whileuseful copolymers include nylon 4,6, poly(hexamethylene adipamide)(nylon 6,6), poly(hexamethylene sebacamide) (nylon 6,10),poly(heptamethylene pimelamide) (nylon 7,7), poly(octamethylenesuberamide) (nylon 8,8), poly(hexamethylene azelamide) (nylon 6,9),poly(nonamethylene azelamide) (nylon 9,9), poly(decamethylene azelamide)(nylon 10,9), poly(tetramethylenediamine-co-oxalic acid) (nylon 4,2),the polyamide of n-dodecanedioic acid and hexamethylenediamine (nylon6,12), the polyamide of dodecamethylenediamine and n-dodecanedioic acid(nylon 12,12) and the like. Other useful aliphatic polyamide copolymersinclude caprolactam/hexamethylene adipamide copolymer (nylon 6,6/6),hexamethylene adipamide/caprolactam copolymer (nylon 6/6,6),trimethylene adipamide/hexamethylene azelaiamide copolymer (nylontrimethyl 6,2/6,2), hexamethylene adipamide-hexamethylene-azelaiamidecaprolactam copolymer (nylon 6,6/6,9/6) and the like. Also included areother nylons which are not particularly delineated here.

Of these polyamides, preferred polyamides include nylon 6, nylon 6,6,nylon 6/6,6 as well as mixtures of the same. Of these, nylon 6 is mostpreferred.

Aliphatic polyamides used in the practice of this invention may beobtained from commercial sources or prepared in accordance with knownpreparatory techniques. For example, poly(caprolactam) can be obtainedfrom Honeywell International Inc., Morristown, N.J.

Exemplary of aliphatic/aromatic polyamides includepoly(tetramethylenediamine-co-isophthalic acid) (nylon 4,I),polyhexamethylene isophthalamide (nylon 6,I), hexamethyleneadipamide/hexamethylene-isophthalamide (nylon 6,6/6I), hexamethyleneadipamide/hexamethyleneterephthalamide (nylon 6,6/6T), poly(2,2,2-trimethyl hexamethylene terephthalamide), poly(m-xylyleneadipamide) (MXD6), poly(p-xylylene adipamide), poly(hexamethyleneterephthalamide), poly(dodecamethylene terephthalamide), polyamide6T/6I, polyamide 6/MXDT/I, polyamide MXDI, and the like. Blends of twoor more aliphatic/aromatic polyamides can also be used.Aliphatic/aromatic polyamides can be prepared by known preparativetechniques or can be obtained from commercial sources.

Other suitable polyamides are described in U.S. Pat. Nos. 4,826,955 and5,541,267, which are incorporated herein by reference.

Suitable cyclic(cyclo)olefin polymers (homopolymers, copolymers orblends) are described, for example, in U.S. Pat. Nos. 5,218,049;5,783,273 and 5,912,070, which are incorporated herein by reference.U.S. Pat. No. 5,218,049 discloses films composed of cyclic olefins. U.S.Pat. No. 5,783,273 discloses press-through blister packaging materialscomprising a sheet of a cyclic olefin copolymer. U.S. Pat. No. 5,912,070discloses a packaging material comprising a layer of a cyclic olefin, alayer of a polyester and an intermediate adhesive. In the most preferredembodiment of the invention, the thermoplastic polymer layer 14comprises a cyclic olefin copolymer. Cyclic olefins may be obtainedcommercially from Mitsui Petrochemical Industries, Ltd. of Tokyo, Japan,or Ticona of Summit, N.J.

The use of a cyclic olefin copolymer (COC) is advantageous because ofits attractive properties. Cyclic olefin copolymers are amorphous,clear, random copolymers. They combine excellent optical and electricalproperties with low density and moisture absorption, with high stiffnessand strength. Some of the beneficial properties of COC's include a highmoisture barrier, low moisture absorption, high light transmission, lowbirefringence, high stiffness and strength. In addition, COC's exhibitgood heat sealability and excellent heat resistance properties,dimensional stability, easy metallizability, ready processability inconventional injection molding, film extrusion, blow molding andthermoforming techniques, and good compatibility with othernon-fluorinated polymers.

The adhesive tie layer 16 preferably comprises a combination of at leastone tackifier and at least one ethylene/alpha-olefin copolymer.Combinations of said adhesive components include blends of saidcomponents. As used herein, a tackifier is intended to describe amaterial that improves the tackiness or stickiness of an adhesivewithout the formation of chemical bonds. Preferred tackifiers ortackifier blends preferably have an interlayer bond strength of at leastabout 45 g/cm, as determined by the ASTM F904 method. Suitabletackifiers non-exclusively include terpene-based polymers,coumarone-based polymers, phenol-based polymers, rosin-based polymers,rosin esters and hydrogenated rosin esters, petroleum and hydrogenatedpetroleum-based polymers, styrene-based polymers and mixtures thereof.

Suitable terpene-based polymers include terpene polymers ofalpha-pinene, beta-pinene, dipentel, limonene, myrcene, bomylene andcamphene, and phenol-modified terpene-based polymers obtained bymodifying these terpene-based polymers with phenols.

Suitable coumarone-based polymers include, for example, coumarone-indenepolymers and phenol-modified coumarone-indene polymers.

Suitable phenol-based polymers include reaction products of phenols suchas phenol, cresol, xylenol, resorcinol, p-tert-butylphenol, andp-phenylphenol with aldehydes such as formaldehyde, acetaldehyde andfurfural, and rosin-modified phenol polymers.

Suitable rosin-based polymers include unmodified rosin (e.g., wood, gum,or tall oil) and rosin derivatives. Rosin-based polymers can beclassified by their rosin acids, which are either an abietic acid or apimaric acid. Abietic acid-type rosins are preferred. Rosin derivativesinclude polymerized rosin, disproportionated rosin, hydrogenated rosin,and esterified rosin. Representative examples of such rosin derivativesinclude pentaerythritol esters of tall oil, gum rosin, wood rosin, ormixtures thereof.

Suitable petroleum and hydrogenated petroleum-based polymers includealiphatic petroleum polymers, alicyclic petroleum polymers, aromaticpetroleum polymers using styrene, alpha-methylstyrene, vinyltoluene,indene, methylindene, butadiene, isoprene, piperylene and pentylene asraw materials, and homopolymers or copolymers of cyclopentadiene.Preferable petroleum polymers include aliphatic hydrocarbon polymers andhydrogenated polycyclodienic polymers. A wide range of unsaturatedcyclic monomers can be obtained from petroleum derivatives, such as, forexample, cyclopentene derivatives, cyclopentadiene derivatives,cyclohexene derivatives, cyclohexadiene derivatives, and the like. Awide range of unsaturated monomers can be obtained from petroleumderivatives, such as, for example, ethylene derivatives, propylenederivatives, butadiene derivatives, isoprene derivatives, pentenes,hexenes, heptenes, and the like.

Suitable styrene-based polymers include homopolymers which are lowmolecular weight polymers comprising styrene as a principal component,and copolymers of styrene with, for example, alpha-methylstyrene,vinyltoluene, and butadiene rubber.

The most preferred tackifiers are terpene-based polymers, petroleum andhydrogenated petroleum-based polymers.

In the preferred embodiment of the invention, the tackifier preferablycomprises from greater than about 1% by weight to about 60% by weight ofsaid tackifier-ethylene/alpha-olefin copolymer combination, morepreferably from about 5% by weight to about 30% by weight, and mostpreferably from about 15% by weight to about 25% by weight. Accordingly,said ethylene/alpha-olefin copolymer preferably comprises from about 40%by weight to about 99% by weight of said tackifier-ethylene/alpha-olefincopolymer combination, more preferably from about 70% by weight to about95% by weight and most preferably from about 75% by weight to about 85%by weight.

The ethylene/alpha-olefin copolymers of the adhesive composition aregenerally characterized as plastomers. In general, plastomers arecomprised of polymerized, random copolymers of ethylene and one or moreolefin comonomers.

Suitable ethylenes which may comprise the ethylene component of theethylene/alpha-olefin copolymer preferably include polyethylenes such aslow density polyethylene, ultra low density polyethylene, linear lowdensity polyethylene, metallocene linear low density polyethylene,medium density polyethylene or high density polyethylene. Preferredethylenes include polyethylene graft copolymers and linear and lowdensity polyethylene copolymers.

Suitable olefins which may be copolymerized with an ethylene to form theethylene/alpha-olefin copolymer include linear and branchedalpha-olefins having 3 to 20 carbon atoms of which preparations aredescribed, for example, in U.S. Pat. Nos. 3,645,992, 5,272,236,5,278,272 and 6,319,979. Specific examples of the linear alpha-olefinsare propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridocene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodeceneand 1-eicocene. Specific examples of the branched alpha-olefins are3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-ethyl-1-hexene and 2,2,4-trimethyl-1-pentene. Of these, linearpropylene, 1-butene, 1-pentene, 1-hexene, 1-octene and 1-decene arepreferred. These alpha-olefins may be used singularly or in combination.

In the preferred embodiment of the invention, the ethylene/alpha-olefincopolymer comprises a copolymer comprising an ethylene and at least onealpha-olefin having from three to twenty carbon atoms (C₃-C₂₀). Forexample, the ethylene/alpha-olefin copolymer may comprise a copolymer ofa linear low density polyethylene and a C₃-C₂₀ alpha-olefin, aterpolymer comprising ethylene and more than one C₃-C₂₀ alpha-olefin ora polyethylene graft copolymer including at lease one C₃-C₂₀alpha-olefin.

In accordance with the present invention, suitable ethylene/alpha-olefincopolymers include modified compositions having at least one functionalmoiety selected from the group consisting of unsaturated polycarboxylicacids and anhydrides thereof. Such unsaturated carboxylic acid andanhydrides include maleic acid and anhydride, fumaric acid andanhydride, crotonic acid and anhydride, citraconic acid and anhydride,itaconic acid and anhydride and the like. Of these, the most preferredis maleic anhydride. In accordance with the invention, modifiedethylene/alpha-olefin copolymer compositions preferably comprise fromabout 0.001 to about 20 percent by weight of the functional moiety,based on the total weight of the modified plastomer. More preferably thefunctional moiety comprises from about 0.05 to about 10 percent byweight, and most preferably from about 0.1 to about 5 percent by weightof the functional moiety. In the preferred embodiment of the invention,the ethylene/alpha-olefin copolymer is unmodified. However, a modifiedethylene/alpha-olefin copolymer is preferred when said thermoplasticpolymer layer comprises a polar material such as nylon or polyester.

In the preferred embodiment of the invention, the ethylene/alpha-olefincopolymers preferably have an ethylene content of from about 35 mole %to about 99.5 mole %, more preferably from about 70 mole % to about 90mole % and most preferably from about 75 mole % to about 85 mole %.Accordingly, the ethylene/alpha-olefin copolymers of the inventionpreferably have an alpha-olefin content of from about 0.5 mole % toabout 65 mole %, more preferably from about 10 mole % to about 30 mole %and most preferably from about 15 mole % to about 25 mole %.

The adhesive tie layer 16 may further include at least one styrenicblock copolymer. The styrenic block copolymer is preferably a styreniccopolymer selected from the group consisting of astyrene/ethylene-propylene/styrene block copolymer (SEPS), astyrene/ethylene ethylene-propylene random/styrene block copolymer(SEEPS), a styrene/butadiene/styrene block copolymer (SBS), astyrene/ethylene butylene random/styrene block copolymer (SEBS), astyrene/isobutylene/styrene block copolymer (SIBS), astyrene/isoprene/styrene block copolymer (SIS), a styrene/hydrogenatedbutylene/styrene block copolymer (SHBS) and a maleic anhydride graftedstyrene/ethylene butylene/styrene copolymer (MAH-g-SEBS). Styrenic blockcopolymers are available in either a diblock type or the more commontriblock types and mixtures thereof. If included, said styrenic blockcopolymer preferably comprises from about 0.1% by weight to about 80% byweight of said adhesive combination, more preferably from about 0.5% byweight to about 15% by weight and most preferably from about 1% byweight to about 6% by weight. The preferred styrenic block copolymersare styrene/isoprene/styrene block copolymer and styrene/ethylenebutylene random/styrene block copolymer. Of these,styrene/isoprene/styrene block copolymer is the most preferred.

As illustrated in FIG. 3 and FIG. 4, the multilayered structures whichare formed into the shaped articles 10 described herein may furthercomprise at least one additional polymer layer 18 that may be attachedon the outer surface of the outer thermoplastic polymer layer 14. Saidat least one additional polymer layer 18 may comprise a layer of anymaterial described herein, but is by no means limited to such materials.For example, optional layer or layers 18 may comprise a layer of afluoropolymer, a polyamide, a polyolefin, an ethylene vinyl acetatecopolymer, polyethylene terephthalate, polyvinyl chloride,polyvinylidene chloride, polystyrene, styrenic copolymers, polyisoprene,polyurethanes, an ethylene acrylic acid polymer, a cyclic olefinhomopolymer or copolymer and combinations thereof. As seen in FIG. 4,the multilayered structure may include a plurality of additional layers18. Said at least one additional layer 18 is preferably, but notnecessarily, attached to the other layers of the structure via anotheradhesive tie layer 16 formed from said adhesive combination.

Each of the inner or the central fluoropolymer layer 12, adhesive tielayer 16, outer thermoplastic polymer layer 14 and any additional layersmay optionally also include one or more conventional additives whoseuses are well known to those skilled in the art. The use of suchadditives may be desirable in enhancing the processing of thecompositions as well as improving the products or articles formedtherefrom. Examples of such include: oxidative and thermal stabilizers,lubricants, release agents, flame-retarding agents, oxidationinhibitors, oxidation scavengers, dyes, pigments and other coloringagents, ultraviolet light absorbers and stabilizers, organic orinorganic fillers including particulate and fibrous fillers, reinforcingagents, nucleators, plasticizers, as well as other conventionaladditives known to the art. Such may be used in amounts, for example, ofup to about 30% by weight of the overall layer composition. It is alsopreferred that no layer of the structure contains a tackifiercomposition but for layers that are labeled as adhesive tie layers. Itis particularly preferred that neither of the outermost layers of thestructures described herein contain a tackifier composition as definedherein. Representative ultraviolet light stabilizers include varioussubstituted resorcinols, salicylates, benzotriazoles, benzophenones, andthe like. Suitable lubricants and release agents include wax, stearicacid, stearyl alcohol, and stearamides. Exemplary flame-retardantsinclude organic halogenated compounds, including decabromodiphenyl etherand the like as well as inorganic compounds. Suitable coloring agentsincluding dyes and pigments include cadmium sulfide, cadmium selenide,titanium dioxide, phthalocyanines, ultramarine blue, nigrosine, carbonblack and the like. Representative oxidative and thermal stabilizersinclude the Period Table of Element's Group I metal halides, such assodium halides, potassium halides, lithium halides; as well as cuproushalides; and further, chlorides, bromides, iodides. Also acceptable arehindered phenols, hydroquinones, aromatic amines as well as substitutedmembers of those above mentioned groups and combinations thereof.Exemplary plasticizers include lactams such as caprolactam and lauryllactam, sulfonamides such as o,p-toluenesulfonamide and N-ethyl, N-butylbenylenesulfonamide, and combinations of any of the above, as well asother plasticizers known to the art.

The multilayered structures of the invention are formed into shapedarticles 10 suitable for storing a product 20. The shaped articles 10 ofthe invention may be produced by conventional methods known in the art,including well known injection molding, co-injection blow molding,co-injection stretch-blow molding or co-extrusion blow moldingtechniques and by forming the structure around a suitable mold andheating in a method well known in the art.

The most preferred method for producing the shaped articles 10 of theinvention is co-extrusion blow molding. Co-extrusion blow molding is aprocess in which individual extruders feed the individual componentsinto a co-extrusion head, where a multi-layer parison is formed andextruded. The parison, still in its melt form, is then sandwichedbetween two mold halves. Once the mold halves have fully closed on theparison, air is introduced into the center of the parison which in turnexpands the parison into the configuration of the mold cavity. Thematerial then solidifies due to lower temperatures introduced from thesurface of the chilled mold halves. The mold halves are then opened upand the newly formed container is ejected from the mold.

Alternately, the shaped articles 10 may be formed by first combining theindividual layers described herein to form a multilayered film, followedby subsequently shaping the multilayered film into a desired shapedarticle 10. In this embodiment, multilayered films may be produced byconventional methods useful in producing multilayer films, includingcoextrusion and lamination techniques. In a conventional coextrusionprocess, the polymeric material for the individual layers are fed intoinfeed hoppers of a like number of extruders, each extruder handling thematerial for one or more of the layers. The melted and plasticatedstreams from the individual extruders are directly fed to amulti-manifold die and then juxtaposed and combined into a layeredstructure or combined into a layered structure in a combining block andthen fed into a single manifold or multi-manifold co-extrusion die. Thelayers emerge from the die as a single multiple layer film of polymericmaterial. After exiting the die, the film is cast onto a firstcontrolled temperature casting roll, passes around the first roll, andthen onto a second controlled temperature roll. The controlledtemperature rolls largely control the rate of cooling of the film afterit exits the die. Additional rolls may be employed. In another method,the film forming apparatus may be one which is referred to in the art asa blown film apparatus and includes a multi-manifold circular die headfor bubble blown film through which the plasticized film composition isforced and formed into a film bubble which may ultimately be collapsedand formed into a film. Typical coextrusion techniques are described inU.S. Pat. Nos. 5,139,878 and 4,677,017. One advantage of coextrudedfilms is the formation of a multilayer film in a one process step bycombining molten layers of each of the film layers, as well as any otheroptional film layers, into a unitary film structure.

Alternately, the individual layers may first be formed as separatelayers and then laminated together under heat and pressure with orwithout intermediate adhesive layers. Lamination techniques are wellknown in the art. Typically, laminating is done by positioning theindividual layers on one another under conditions of sufficient heat andpressure to cause the layers to combine into a unitary film. Typicallythe fluoropolymer layer, the thermoplastic polymer layer, the adhesiveand any additional layers are positioned on one another, and thecombination is passed through the nip of a pair of heated laminatingrollers by techniques well known in the art. Lamination heating may bedone at temperatures ranging from about 120° C. to about 175° C.,preferably from about 150° C. to about 175° C., at pressures rangingfrom about 5 psig (0.034 MPa) to about 100 psig (0.69 MPa), for fromabout 5 seconds to about 5 minutes, preferably from about 30 seconds toabout 1 minute. In the preferred embodiment of the invention, the shapedarticles 10 are formed by co-extrusion blow molding.

In the embodiment where the multilayered structure of the invention isformed into a film prior to being molded into a shaped article 10, thefilm may be uniaxially or biaxially oriented prior to molding. Thelayers may be drawn to a draw ratio of from 1.5:1 to 5:1 uniaxially inat least one direction, i.e. its longitudinal direction, its transversedirection or biaxially in each of its longitudinal and transversedirections. For the purposes of the present invention the term drawratio is an indication of the increase in the dimension in the directionof draw. For example, the multilayered structure may be uniaxiallyoriented from about 1.3 to about 10 times in either its longitudinal ortransverse directions, or the multilayered structure may be biaxiallyoriented from about 1.5 to about 5 times each of its longitudinal andtransverse directions. The structure may also be drawn to a lesser orgreater degree in either or both of said longitudinal and transversedirections. The layers may be simultaneously biaxially oriented, forexample orienting a film in both the machine and transverse directionsat the same. This results in dramatic improvements in clarity, strengthand toughness properties, as well as an improved moisture vaportransmission rate.

Although each layer of the multilayer structures may have a differentthickness, the fluoropolymer layer 12 has a preferred thickness of fromabout 0.01 mil (0.25 μm) to about 20 mil (508 μm), more preferably fromabout 0.1 mil (2.5 μm) to about 10 mil (254 μm), and most preferablyfrom about 0.3 mil (7.6 μm) to about 6 mil (152 μm). The thermoplasticpolymer layer 14 has a thickness of about 0.04 mil (1 μm) to about 200mil (5080 μm), a preferred thickness of from about 2 mil (50 μm) toabout 100 mil (2540 μm), more preferably from about 5 mil (127 μm) toabout 60 mil (1520 μm). The adhesive tie layers have a preferredthickness of from about 0.04 mil (1 μm) to about 20 mil (508 μm), morepreferably from about 0.3 mil (7.6 μm) to about 10 mil (254 μm).Additional layers preferably have a thickness of from about 0.04 mil (1μm) to about 200 mil (5080 μm), more preferably from about 0.4 mil (10μm) to about 100 mil (2540 μm) and most preferably from about 0.8 mil(20 μm) to about 60 mil (1520 μm). While such thicknesses arereferenced, it is to be understood that other layer thicknesses may beproduced to satisfy a particular need and yet fall within the scope ofthe present invention.

The moisture vapor transmission rate (MVTR) of such structures of theinvention may be determined via the procedure set forth in ASTM F1249.In the preferred embodiment, the structures of the invention have apreferred MVTR of from about 1.0 or less g/100 in²/day (15.5 g/m²/day)of the overall structure at 37.8° C. and 100% relative humidity (RH),more preferably from 0.0005 to about 0.7 g/100 in²/day (0.0077 to about10.7 g/m²/day) of the overall structure, and most preferably from 0.001to about 0.06 g/100 in²/day (0.015 to about 0.93 g/m²/day) of theoverall structure, as determined by water vapor transmission ratemeasuring equipment available from, for example, Mocon.

The oxygen transmission rate (OTR) of the structures of the inventionmay be determined via the procedure of ASTM D-3985 using an OX-TRAN 2/20instrument manufactured by Mocon, operated at 25° C., 0% RH. In thepreferred embodiment, the overall structure of the invention has apreferred OTR of from about 50 or less cc/100 in²/day (775 g/m²/day),more preferably from about 0.001 to about 20 cc/100 in²/day (0.015 toabout 310 g/m²/day), and most preferably from about 0.001 to about 10cc/100 in²/day (0.015 to about 150 cc/m²/day).

The shaped articles of the invention are useful for a variety of endapplications, such as for medical packaging, pharmaceutical packaging,packaging of other moisture sensitive products and other industrialuses, particularly as bottles for packaging liquid or solid food orpharmaceutical products. As described herein, two alternate embodimentsof the invention are presented. As FIG. 1 and FIG. 2 illustrate, theshaped articles 10 may be formed such that the fluoropolymer layer ofthe multilayered structure is the innermost layer of the article and theclosest layer of the structure to said product. Alternately, asillustrated in FIG. 6, the shaped articles 10 may be formed such thatthe fluoropolymer is a central layer of the structure, being positionedbetween a pair of adhesive layers 16 and a pair of outer thermoplasticpolymer layers 14. Regardless of the construction, the articles orbottles formed therefrom exhibit excellent interlayer bond strengthbetween the inner or central fluoropolymer layer and an adjacentthermoplastic polymer layer. Such articles are lightweight,non-breakable structures with good clarity, a high moisture barrier,good chemical resistance and low water vapor and gas transmissionproperties. Accordingly, such articles are particularly well suited forstoring and increasing the shelf life of such moisture sensitiveproducts.

The following non-limiting examples serve to illustrate the invention.

EXAMPLE 1 (COMPARATIVE)

A three-layer HDPE/PCTFE/HDPE (Unival DMDA-6220 from Dow Plastics/Aclon™1180 from Honeywell International/Unival DMDA-6220 NT7 from DowPlastics) bottle was prepared in a multilayer coextrusion blow-moldingoperation. The PCTFE (density: 2.11 g/cm³; viscosity: 82 zst; DSCmelting point: 211° C.) and the HDPE (density: 0.953 g/cm³; melt index(ASTM D1238): 0.38 g/10 minutes at 190° C. and 2.16 kg load; DSC meltingpoint: 131° C.) were simultaneously extruded. Six single screw extruderswere involved in the operation. The dimensions of the involved extrudersand a set of extrusion conditions are listed in Table 1. Molten materialfrom Extruder 1 went into the die head and was formed into a circulardownstream around the blow pin at the die head gradually gaining layerswith materials in order of extruder number on the way to the die exit. Alayered circular molten parison, having a cross sectional area of 4.9cm², was pumped out at the die exit into a mold and blown out to fill upa cavity of a mold of a rotary mold system which rotated at 3 rpm. Across-sectional area of the cavity of 20.7 cm long increased graduallyin the bottle neck zone of 9 cm long, changing the shape of the crosssection from a circle to an oval. A cross section below the bottle neckis an oval rectangle whose minimum and maximum diagonal distances, crosssectional area, and height were 5 cm and 8.7 cm, 39 cm², and 11.7 cm,respectively. The temperature of the mold was constantly maintained at10° C. throughout the operation. TABLE 1 Equipment, Material andProcessing Conditions Extruder # EXT 1 EXT 2 EXT 3 EXT 4 EXT 5 EXT 6Screw Diameter (mm) 50.8 31.8 38.1 31.8 50.8 50.8 SpecificationLength/Diameter 24/1 24/1 24/1 24/1 24/1 24/1 Ratio Resin HDPE HDPEPCTFE HDPE HDPE HDPE Temperature Barrel Zone 1 191 191 232 191 191 191(° C.) Barrel Zone 2 204 204 288 204 204 204 Barrel Zone 3 204 204 288204 204 204 Elbow Connector 204 204 288 204 204 204 Transfer Pipe 204204 288 204 204 204 Die Head 210 210 210 210 210 210 Screw Speed (rpm)28 15 12 15 28 28

The resulting three layer (HDPE/PCTFE/HDPE) bottle had a gauge profileof about 254 μm/25 μm/457 μm from inside to outside when they were takenfrom the wider side of the fully blown oval rectangle zone below thebottle neck. The resulting total thickness of the sample was about 736μm. The interlayer bond strength of the resulting three-layer(HDPE/PCTFE/HDPE) bottle was determined by using a standard ASTM testingmethod (ASTM F904). The test was done at a constant cross head speed of30.48 cm/min with the un-separated portion of the specimen supported at90° to the direction of the draw. No considerable bond strength (˜0g/2.54 cm) was found between HDPE and PCTFE layers from anywhere of thebottle.

EXAMPLE 2

A five-layer HDPE/tie layer/PCTFE/tie layer/HDPE (Unival DMDA-6220 fromDow Plastics/Admer™ SF600 from Mitsui Chemicals/Aclon™ 1180 fromHoneywell/Admer™ SF600 from Mitsui Chemical/Unival DMDA-6220 NT7 fromDow Plastics) bottle was prepared in a multilayer coextrusionblow-molding operation. The Admer™ SF600 (density: 0.088 g/cm³; meltindex (ASTM D1238): 3.5 g/10 minutes at 190° C. and 2.16 kg load; Vicatsoftening point (ASTM D1525): lower than 40° C.) was simultaneouslyextruded as a tie layer between HDPE and PCTFE layers under a set ofconditions listed in Table 2. The Admer™ SF600 is a mixture ofethylene-propylene copolymer modified with maleic anhydride and atackifier. All the other machine settings and processing parameters notspecified in Table 2 were the same as those in Example 1. TABLE 2Equipment, Material and Processing Conditions Extruder # EXT 1 EXT 2 EXT3 EXT 4 EXT 5 EXT 6 Screw Diameter (mm) 50.8 31.8 38.1 31.8 50.8 50.8Specification Length/Diameter 24/1 24/1 24/1 24/1 24/1 24/1 Ratio ResinHDPE tie layer ACLON tie layer HDPE HDPE Temperature Barrel Zone 1 191135 232 135 191 191 (° C.) Barrel Zone 2 204 199 288 199 204 204 BarrelZone 3 204 232 288 232 204 204 Elbow Connector 204 232 288 232 204 204Transfer Pipe 204 232 288 232 204 204 Die Head 210 210 210 210 210 210Screw Speed (rpm) 28 20 12 20 28 28

The five-layer (HDPE/tie layer/PCTFE/tie layer/HDPE) bottle showed agauge profile of about 229 μm /51 μm /25 μm /51 μm/432 μm from inside tooutside when they were taken from the wider side of the fully blown ovalrectangle zone below the bottle neck. The resulting total thickness ofthe zone was about 788 μm. Interlayer bond strength between HDPE andPCTFE layer in the five layer (HDPE/tie layer/PCTFE/tie layer/HDPE)bottle was determined by using a standard ASTM testing method (ASTMF904). The testing method was described in Example 1. The resultinginterlayer bond strength between HDPE and PCTFE layers of the wider sideof the fully blown oval rectangle zone was about 1600 g/2.54 cm.

1. A shaped article for storing a product, said shaped article beingformed from a multilayered structure which comprises in sequence: a) aninner fluoropolymer layer having first and second surfaces; b) anadhesive tie layer, having first and second surfaces, on the innerfluoropolymer layer with the first surface of the adhesive tie layer onthe first surface of the fluoropolymer layer; which adhesive tie layercomprises a combination of at least one tackifier, at least oneethylene/alpha-olefin copolymer and optionally at least one styrenicblock copolymer; and c) an outer thermoplastic polymer layer, havingfirst and second surfaces, on the adhesive tie layer with the firstsurface of the thermoplastic polymer layer on the second surface of theadhesive tie layer.
 2. The shaped article of claim 1 further comprisingat least one polymer layer on the second surface of the thermoplasticpolymer layer.
 3. The shaped article of claim 2 wherein said at leastone polymer layer is attached to the second surface of the thermoplasticpolymer layer via an adhesive tie layer which comprises a combination ofat least one tackifier, at least one ethylene/alpha-olefin copolymer andoptionally at least one styrenic block copolymer.
 4. The shaped articleof claim 2 further comprising a plurality of polymer layers attached tothe second surface of the thermoplastic polymer layer via an adhesivetie layer which comprises a combination of at least one tackifier, atleast one ethylene/alpha-olefin copolymer and optionally at least onestyrenic block copolymer.
 5. The shaped article of claim 2 wherein saidat least one polymer layer comprises a material selected from the groupconsisting a fluoropolymer, a polyamide, a polyolefin, an ethylene vinylacetate copolymer, polyethylene terephthalate, polyvinyl chloride,polyvinylidene chloride, polystyrene, styrenic copolymers, polyisoprene,polyurethanes, polystyrene, a styrenic copolymer, an ethylene acrylicacid copolymer, a cyclic olefin homopolymer or copolymer andcombinations thereof.
 6. The shaped article of claim 1 wherein saidinner fluoropolymer layer comprises a material selected from the groupconsisting of a chlorotrifluoroethylene homopolymer, anethylene-chlorotrifluoroethylene copolymer, ethylene-tetrafluoroethylenecopolymer, fluorinated ethylene-propylene copolymer,perfluoroalkoxyethylene, polytetrafluoroethylene, polyvinyl fluoride,polyvinylidene fluoride, poly(chlorotrifluoroethylene) or apoly(chlorotrifluoroethylene) containing copolymer, and copolymers andblends thereof.
 7. The shaped article of claim 1 wherein said innerfluoropolymer layer comprises poly(chlorotrifluoroethylene).
 8. Theshaped article of claim 1 wherein said outer thermoplastic polymer layercomprises a material selected from the group consisting of linear orbranched polyolefin homopolymers, linear or branched polyolefincopolymers, cyclic olefin homopolymers, copolymers of cyclic olefins andlinear or branched polyolefin homopolymers, copolymers of cyclic olefinsand linear or branched polyolefin copolymers, ethylene vinyl acetatecopolymers, polyesters such as polyethylene terephthalate, polyamides,polyvinyl chloride, polyvinylidene chloride, polystyrene, styreniccopolymers, polyisoprene, polyurethanes, ethylene ethyl acrylate,ethylene acrylic acid copolymers, fluoropolymers and combinationsthereof.
 9. The shaped article of claim 1 wherein said outerthermoplastic layer comprises a homopolymer or copolymer containing alow density polyethylene, linear low density polyethylene, ultra lowdensity polyethylene, metallocene linear low density polyethylene,medium density polyethylene, high density polyethylene, polypropylene orpolybutylene, or a blend thereof.
 10. The shaped article of claim 1wherein said at least one tackifier comprises a material selected fromthe group consisting of terpene-based polymers, coumarone-basedpolymers, phenol-based polymers, rosin-based polymers, rosin esters andhydrogenated rosin esters, petroleum and hydrogenated petroleum-basedpolymers, styrene-based polymers and mixtures thereof.
 11. The shapedarticle of claim 1 wherein said at least one tackifier is selected fromthe group consisting of terpene-based polymers, petroleum andhydrogenated petroleum-based polymers.
 12. The shaped article of claim 1wherein said ethylene/alpha-olefin copolymer comprises a copolymercomprising an ethylene and at least one alpha-olefin having from threeto twenty carbon atoms (C₃-C₂₀).
 13. The shaped article of claim 1wherein said adhesive tie layer further comprises at least one styrenicblock copolymer.
 14. The shaped article of claim 1 which is formed byco-extrusion blow molding.
 15. The shaped article of claim 1 whichfurther comprises a moisture sensitive product enclosed within theshaped article, wherein said product is adjacent to said innerfluoropolymer layer.
 16. The shaped article of claim 1 which is abottle.
 17. A shaped article for storing a product, said shaped articlebeing formed from a multilayered structure which comprises in sequence:a) an inner poly(chlorotrifluoroethylene) layer having first and secondsurfaces; b) an adhesive tie layer, having first and second surfaces, onthe inner poly(chlorotrifluoroethylene) layer with the first surface ofthe adhesive tie layer on the first surface of thepoly(chlorotrifluoroethylene) layer; which adhesive tie layer comprisesa combination of at least one tackifier, at least oneethylene/alpha-olefin copolymer and optionally at least one styrenicblock copolymer; c) a polyethylene layer, having first and secondsurfaces, on the adhesive tie layer with the first surface of thepolyethylene layer on the second surface of the adhesive tie layer; andd) at least one polymer layer on the second surface of the polyethylenelayer.
 18. The shaped article of claim 17 wherein said adhesive tielayer further comprises at least one styrenic block copolymer.
 19. Theshaped article of claim 17 which is formed by co-extrusion blow molding.20. The shaped article of claim 17 which further comprises a moisturesensitive product enclosed within the shaped article, wherein saidproduct is adjacent to said inner fluoropolymer layer.
 21. The shapedarticle of claim 17 which is a bottle.
 22. A process for forming ashaped article for storing a product which comprises: I) forming amultilayered structure by a process which comprises: a) forming an innerfluoropolymer layer having first and second surfaces; b) attaching anadhesive tie layer, having first and second surfaces, to thefluoropolymer layer with the first surface of the adhesive tie layer onthe first surface of the fluoropolymer layer; which adhesive tie layercomprises a combination of at least one tackifier, at least oneethylene/alpha-olefin copolymer and optionally at least one styrenicblock copolymer; c) attaching an outer thermoplastic polymer layer,having first and second surfaces, to the adhesive tie layer with thefirst surface of the thermoplastic polymer layer on the second surfaceof the adhesive tie layer; and II) forming said multilayered structureinto an article by injection molding, blow molding, co-injection blowmolding, co-injection stretch-blow molding or co-extrusion blow moldingtechniques.
 23. The process of claim 22 wherein said adhesive tie layerfurther comprises at least one styrenic block copolymer.
 24. The processof claim 22 wherein said shaped article is formed by co-extrusion blowmolding.
 25. The process of claim 22 wherein said multilayered structureis formed into a bottle.
 26. The process of claim 22 wherein saidprocess for forming a multilayered structure further comprises the stepof attaching at least one polymer layer on the second surface of thethermoplastic polymer layer.
 27. A shaped article for storing a product,said shaped article being formed from a multilayered structure whichcomprises in sequence: a) a first outer thermoplastic polymer layer,having first and second surfaces; b) a first adhesive tie layer, havingfirst and second surfaces, on the first outer thermoplastic layer withthe first surface of the first adhesive tie layer on the first surfaceof the first outer thermoplastic polymer layer; which first adhesive tielayer comprises a combination of at least one tackifier, at least oneethylene/alpha-olefin copolymer and optionally at least one styrenicblock copolymer; and c) a central fluoropolymer layer having first andsecond surfaces, on the first adhesive tie layer with the first surfaceof the central fluoropolymer layer on the second surface of the firstadhesive tie layer; d) a second adhesive tie layer, having first andsecond surfaces, on the central fluoropolymer layer with the firstsurface of the second adhesive tie layer on the first surface of thecentral fluoropolymer layer; which second adhesive tie layer comprises acombination of at least one tackifier, at least oneethylene/alpha-olefin copolymer and optionally at least one styrenicblock copolymer; and e) a second outer thermoplastic polymer layer,having first and second surfaces, on the second adhesive tie layer withthe first surface of the second outer thermoplastic polymer layer on thesecond surface of the second adhesive tie layer.
 28. The shaped articleof claim 27 wherein said central fluoropolymer layer comprises amaterial selected from the group consisting of a chlorotrifluoroethylenehomopolymer, an ethylene-chlorotrifluoroethylene copolymer,ethylene-tetrafluoroethylene copolymer, fluorinated ethylene-propylenecopolymer, perfluoroalkoxyethylene, polytetrafluoroethylene, polyvinylfluoride, polyvinylidene fluoride, poly(chlorotrifluoroethylene) or apoly(chlorotrifluoroethylene) containing copolymer, and copolymers andblends thereof.
 29. The shaped article of claim 27 wherein said centralfluoropolymer layer comprises poly(chlorotrifluoroethylene).
 30. Theshaped article of claim 27 wherein each of said first and second outerthermoplastic polymer layers comprises a material selected from thegroup consisting of linear or branched polyolefin homopolymers, linearor branched polyolefin copolymers, cyclic olefin homopolymers,copolymers of cyclic olefins and linear or branched polyolefinhomopolymers, copolymers of cyclic olefins and linear or branchedpolyolefin copolymers, ethylene vinyl acetate copolymers, polyesterssuch as polyethylene terephthalate, polyamides, polyvinyl chloride,polyvinylidene chloride, polystyrene, styrenic copolymers, polyisoprene,polyurethanes, ethylene ethyl acrylate, ethylene acrylic acidcopolymers, fluoropolymers and combinations thereof.
 31. The shapedarticle of claim 27 wherein each of said first and second outerthermoplastic layers comprises a homopolymer or copolymer containing alow density polyethylene, linear low density polyethylene, ultra lowdensity polyethylene, metallocene linear low density polyethylene,medium density polyethylene, high density polyethylene, polypropylene orpolybutylene or a blend thereof.
 32. The shaped article of claim 27wherein said adhesive tie layer further comprises at least one styrenicblock copolymer.
 33. The shaped article of claim 27 which is formed byco-extrusion blow molding.
 34. The shaped article of claim 27 whichfurther comprises a moisture sensitive product enclosed within theshaped article, wherein said product is adjacent to said centralfluoropolymer layer.
 35. The shaped article of claim 27 which is abottle.
 36. A shaped article for storing a product, said shaped articlebeing formed from a multilayered structure which comprises in sequence:a) a first outer polyethylene layer, having first and second surfaces;b) a first adhesive tie layer, having first and second surfaces, on thefirst outer polyethylene layer with the first surface of the firstadhesive tie layer on the first surface of the first outer polyethylenelayer; which first adhesive tie layer comprises a combination of atleast one tackifier, at least one ethylene/alpha-olefin copolymer andoptionally at least one styrenic block copolymer; and c) a centralpoly(chlorotrifluoroethylene) layer having first and second surfaces, onthe first adhesive tie layer with the first surface of the centralpoly(chlorotrifluoroethylene) layer on the second surface of the firstadhesive tie layer; d) a second adhesive tie layer, having first andsecond surfaces, on the central poly(chlorotrifluoroethylene) layer withthe first surface of the second adhesive tie layer on the first surfaceof the central poly(chlorotrifluoroethylene) layer; which secondadhesive tie layer comprises a combination of at least one tackifier, atleast one ethylene/alpha-olefin copolymer and optionally at least onestyrenic block copolymer; and e) a second outer polyethylene layer,having first and second surfaces, on the second adhesive tie layer withthe first surface of the second outer polyethylene layer on the secondsurface of the second adhesive tie layer.
 37. The shaped article ofclaim 36 wherein said adhesive tie layer further comprises at least onestyrenic block copolymer.
 38. The shaped article of claim 36 which isformed by co-extrusion blow molding.
 39. The shaped article of claim 36which further comprises a moisture sensitive product enclosed within theshaped article, wherein said product is adjacent to said centralfluoropolymer layer.
 40. The shaped article of claim 36 which is abottle.
 41. The shaped article of claim 36 which further comprises amoisture sensitive product enclosed within the shaped article, whereinsaid product is adjacent to said inner fluoropolymer layer.
 42. Aprocess for forming a shaped article for storing a product whichcomprises: I) forming a multilayered structure by a process whichcomprises: a) forming a first outer thermoplastic polymer layer, havingfirst and second surfaces; b) attaching a first adhesive tie layer,having first and second surfaces, to the first outer thermoplastic layerwith the first surface of the first adhesive tie layer on the firstsurface of the first outer thermoplastic polymer layer; which firstadhesive tie layer comprises a combination of at least one tackifier, atleast one ethylene/alpha-olefin copolymer and optionally at least onestyrenic block copolymer; and c) attaching a central fluoropolymer layerhaving first and second surfaces, to the first adhesive tie layer withthe first surface of the central fluoropolymer layer on the secondsurface of the first adhesive tie layer; d) attaching a second adhesivetie layer, having first and second surfaces, to the centralfluoropolymer layer with the first surface of the second adhesive tielayer on the first surface of the central fluoropolymer layer; whichsecond adhesive tie layer comprises a combination of at least onetackifier, at least one ethylene/alpha-olefin copolymer and optionallyat least one styrenic block copolymer; and e) attaching a second outerthermoplastic polymer layer, having first and second surfaces, to thesecond adhesive tie layer with the first surface of the second outerthermoplastic polymer layer on the second surface of the second adhesivetie layer; and II) forming said multilayered structure into an articleby injection molding, co-injection blow molding, co-injectionstretch-blow molding or co-extrusion blow molding techniques.
 43. Theprocess of claim 42 wherein said adhesive tie layer further comprises atleast one styrenic block copolymer.
 44. The process of claim 42 whereinsaid multilayered structure is formed into a bottle.
 45. The process ofclaim 42 wherein said shaped article is formed by co-extrusion blowmolding.